EP4138159A1 - Particules de matériau actif d'électrode positive pour batterie secondaire au lithium, électrode positive pour batterie secondaire au lithium, et batterie secondaire au lithium - Google Patents
Particules de matériau actif d'électrode positive pour batterie secondaire au lithium, électrode positive pour batterie secondaire au lithium, et batterie secondaire au lithium Download PDFInfo
- Publication number
- EP4138159A1 EP4138159A1 EP21788988.0A EP21788988A EP4138159A1 EP 4138159 A1 EP4138159 A1 EP 4138159A1 EP 21788988 A EP21788988 A EP 21788988A EP 4138159 A1 EP4138159 A1 EP 4138159A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- secondary battery
- positive electrode
- lithium secondary
- particles
- active material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000002245 particle Substances 0.000 title claims abstract description 201
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 155
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 55
- 230000005291 magnetic effect Effects 0.000 claims abstract description 75
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims description 116
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- 239000002889 diamagnetic material Substances 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000002907 paramagnetic material Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 48
- 229910001416 lithium ion Inorganic materials 0.000 description 48
- 238000000034 method Methods 0.000 description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 45
- 238000001354 calcination Methods 0.000 description 43
- 239000007784 solid electrolyte Substances 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 28
- 239000007788 liquid Substances 0.000 description 26
- 230000005292 diamagnetic effect Effects 0.000 description 22
- 239000002243 precursor Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000007773 negative electrode material Substances 0.000 description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 19
- 239000002131 composite material Substances 0.000 description 19
- 239000002905 metal composite material Substances 0.000 description 19
- 229910015118 LiMO Inorganic materials 0.000 description 18
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- 239000004020 conductor Substances 0.000 description 18
- 239000008151 electrolyte solution Substances 0.000 description 18
- 239000012266 salt solution Substances 0.000 description 18
- -1 hydrogen peroxide Chemical class 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 15
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 239000011572 manganese Substances 0.000 description 12
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 11
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 11
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 150000002642 lithium compounds Chemical class 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000010949 copper Substances 0.000 description 10
- 239000008139 complexing agent Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 7
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 7
- 150000002696 manganese Chemical class 0.000 description 7
- 150000002815 nickel Chemical group 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000011163 secondary particle Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 150000001868 cobalt Chemical class 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 5
- 230000005389 magnetism Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
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- 229910052710 silicon Inorganic materials 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229910001216 Li2S Inorganic materials 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003302 ferromagnetic material Substances 0.000 description 4
- 230000005307 ferromagnetism Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910009292 Li2S-GeS2 Inorganic materials 0.000 description 3
- 229910009311 Li2S-SiS2 Inorganic materials 0.000 description 3
- 229910009351 Li2S—GeS2 Inorganic materials 0.000 description 3
- 229910009433 Li2S—SiS2 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 description 3
- 235000011151 potassium sulphates Nutrition 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002885 antiferromagnetic material Substances 0.000 description 2
- 230000005303 antiferromagnetism Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
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- 159000000002 lithium salts Chemical class 0.000 description 2
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- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000005408 paramagnetism Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 229910009303 Li2S-P2S5-LiCl Inorganic materials 0.000 description 1
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- 229910009224 Li2S—P2S5-LiI Inorganic materials 0.000 description 1
- 229910009216 Li2S—P2S5—LiBr Inorganic materials 0.000 description 1
- 229910009237 Li2S—P2S5—LiCl Inorganic materials 0.000 description 1
- 229910009240 Li2S—P2S5—LiI Inorganic materials 0.000 description 1
- 229910007281 Li2S—SiS2—B2S3LiI Inorganic materials 0.000 description 1
- 229910007291 Li2S—SiS2—LiBr Inorganic materials 0.000 description 1
- 229910007288 Li2S—SiS2—LiCl Inorganic materials 0.000 description 1
- 229910007289 Li2S—SiS2—LiI Inorganic materials 0.000 description 1
- 229910007306 Li2S—SiS2—P2S5LiI Inorganic materials 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910010842 LiI—Li2S—P2O5 Inorganic materials 0.000 description 1
- 229910010847 LiI—Li3PO4-P2S5 Inorganic materials 0.000 description 1
- 229910010864 LiI—Li3PO4—P2S5 Inorganic materials 0.000 description 1
- 229910012981 LiVO2 Inorganic materials 0.000 description 1
- 229910006265 Li—La—Zr Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006854 SnOx Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WPQPAQCECMVNAY-UHFFFAOYSA-N acetic acid;1h-pyrimidine-2,4-dione Chemical compound CC(O)=O.CC(O)=O.O=C1C=CNC(=O)N1 WPQPAQCECMVNAY-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004883 computer application Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011357 graphitized carbon fiber Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the CAM particles are composed of secondary particles alone, which are each an aggregate of primary particles.
- the crystal structure of the LiMO is a layered structure and more preferably a hexagonal crystal structure or a monoclinic crystal structure.
- layered structure means a crystal structure in which layers each formed of lithium atoms, transition metal atoms, or oxygen atoms are laminated.
- the crystal structure is particularly preferably a hexagonal crystal structure belonging to the space group R-3m or a monoclinic crystal structure belonging to C2/m.
- the combination of the upper limit value and lower limit value of the average value 0.3 ⁇ m or more and 40 ⁇ m or less, 0.4 ⁇ m or more and 30 ⁇ m or less, and 0.5 ⁇ m or more and 20 ⁇ m or less are exemplary examples.
- the average value is 0.2 ⁇ m or more and 50 ⁇ m or less, lithium ions can migrate smoothly, and it is possible to improve the battery characteristics of the lithium secondary battery.
- the standard deviation of the number-based particle diameters obtained by the measurement of at least 1000 CAM particles is preferably 0.2 ⁇ m or more and 40 ⁇ m or less.
- the combination of the upper limit value and lower limit value of the standard deviation 0.3 ⁇ m or more and 35 ⁇ m or less, 0.4 ⁇ m or more and 30 ⁇ m or less, and 0.5 ⁇ m or more and 20 ⁇ m or less are exemplary examples.
- the standard deviation is 0.2 ⁇ m or more and 40 ⁇ m or less, lithium ions can migrate smoothly, and it is possible to improve the battery characteristics of the lithium secondary battery.
- M represents one or more elements selected from the group consisting of Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga, and V, and -0.1 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.8, 0 ⁇ w ⁇ 0.1, and y + z + w ⁇ 1 are satisfied.
- x is preferably more than 0, more preferably 0.01 or more, and still more preferably 0.02 or more.
- x is preferably 0.1 or less, more preferably 0.08 or less, and still more preferably 0.06 or less.
- the upper limit value and lower limit value of x can be randomly combined together.
- the upper limit value and lower limit value of y can be randomly combined together.
- z is preferably 0.01 or more, more preferably 0.02 or more, and still more preferably 0.04 or more.
- z is preferably 0.4 or less, more preferably 0.35 or less, and still more preferably 0.3 or less.
- An element M corresponds to a paramagnetic material or a diamagnetic material.
- M in the composition formula (1) is one or more elements selected from the group consisting of Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga, and V.
- the paramagnetic material is Ti, Mg, Al, W, Mo, Nb, S, Zr, and V.
- the diamagnetic material is Cu, B, Zn, and Ga.
- M in the composition formula (1) is preferably one or more metals selected from the group consisting of Cu, Ti, Al, Mo, Zn, and Zr.
- the upper limit value and lower limit value of w can be randomly combined together.
- w is preferably 0.001 ⁇ w ⁇ 0.07.
- the MCC containing Ni and the random metal element will be referred to as "precursor".
- a metal composite hydroxide containing a random metal element or a metal composite oxide containing a random metal element is preferable.
- metal composite hydroxides containing Ni, Co, and Mn as metal elements are exemplary examples.
- a nickel salt solution, a cobalt salt solution, a manganese salt solution, and a complexing agent are reacted with one another by a coprecipitation method, particularly, the continuous method described in JP-A-2002-201028 , thereby producing a precursor represented by Ni (1-y-z) Co y Mn z (OH) 2 (in the formula, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.8, and y + z ⁇ 1).
- a nickel salt which is the solute of the nickel salt solution, is not particularly limited, and, for example, any one or more of nickel sulfate, nickel nitrate, nickel chloride, and nickel acetate can be used.
- cobalt salt that is a solute of the cobalt salt solution
- any one or more of cobalt sulfate, cobalt nitrate, cobalt chloride, and cobalt acetate can be used.
- manganese salt that is a solute of the manganese salt solution
- any one or more of manganese sulfate, manganese nitrate, manganese chloride, and manganese acetate can be used.
- the above-described metal salts are used in proportions corresponding to the composition ratio of Ni (1-y-z) Co y Mn z (OH) 2 .
- water is used as the solvent.
- the complexing agent is a compound capable of forming a complex with ions of nickel, cobalt, and manganese in aqueous solutions.
- examples thereof include an ammonium ion feeder, hydrazine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, uracil diacetic acid, and glycine.
- ammonium ion feeder ammonium salts such as ammonium hydroxide, ammonium sulfate, ammonium chloride, ammonium carbonate and ammonium fluoride are exemplary examples.
- the mole ratio of the complexing agent to the sum of the mole numbers of the metal salts is more than 0 and 2.0 or less.
- an alkaline aqueous solution is added to the liquid mixture before the pH of the liquid mixture turns from alkaline into neutral.
- the alkaline aqueous solution sodium hydroxide or potassium hydroxide can be used.
- the pH is measured when the liquid mixture has been heated to reach 40°C.
- the pH is measured when the liquid mixture has been cooled to reach 40°C.
- the pH value in the reaction vessel is controlled in a range of, for example, pH 9 or higher and pH 13 or lower and preferably pH 11 or higher and pH 13 or lower.
- the pH is pH 9 or more and pH 13 or less
- the average value, median value, and standard deviation of the number-based particle diameters of the CAM particles can be controlled to the above-described ranges.
- the temperature of the reaction vessel is controlled in a range of, for example, 20°C or higher and 80°C or lower and preferably 30°C or higher and 70°C or lower.
- the substances in the reaction vessel are appropriately stirred and mixed together.
- reaction vessel that is used in the continuous coprecipitation method, it is possible to use a reaction vessel in which the formed reaction precipitate is caused to overflow for separation.
- the inside of the reaction vessel may be an inert atmosphere.
- inert atmosphere it is possible to suppress the aggregation of elements that are more easily oxidized than Ni and to obtain a homogeneous metal composite hydroxide containing Ni.
- a method for introducing the gas a method in which a predetermined gaseous species is aerated into the reaction vessel and a method in which the liquid mixture is directly bubbled are exemplary examples.
- an inert gas, an oxidizing gas or a gas mixture of an inert gas and an oxidizing gas can be appropriately used.
- the inert gas for example, a nitrogen gas, an argon gas, carbon dioxide, and the like are exemplary examples.
- the oxidizing gas an air and an oxygen gas are exemplary examples.
- a compound that oxidizes the reaction precipitate may be added into the reaction vessel.
- a peroxide such as hydrogen peroxide, a peroxide salt such as permanganate, perchloric acid, hypochlorous acid, nitric acid, halogen, ozone, or the like.
- a compound that reduces the reaction precipitate may be added into the reaction vessel.
- an organic acid such as oxalic acid or formic acid, sulfite, hydrazine, or the like.
- reaction precipitate is washed with water and then dried, whereby the precursor is obtained.
- a nickel cobalt manganese hydroxide as a nickel cobalt manganese composite compound is obtained as the precursor.
- the reaction precipitate may be washed with a weak acid water or an alkaline solution.
- a solution containing sodium hydroxide or potassium hydroxide can be used as the alkaline solution that is used for washing.
- the nickel cobalt manganese composite hydroxide has been produced, but a nickel cobalt manganese composite oxide may be prepared.
- a nickel cobalt manganese composite oxide can be prepared by calcining the nickel cobalt manganese composite hydroxide.
- the total time taken while the temperature begins to be raised and reaches the calcining temperature and the holding of the composite metal hydroxide at the calcining temperature ends is preferably set to one hour or longer and 30 hours or shorter.
- the temperature rising rate in the heating step until the highest holding temperature is reached is preferably 180 °C/hour or faster, more preferably 200 °C/hour or faster, and particularly preferably 250 °C/hour or faster.
- the highest holding temperature in the present specification is the highest temperature of the holding temperature of the atmosphere in a calcining furnace in a calcining step and means the calcining temperature in the calcining step.
- the highest holding temperature means the highest temperature in each heating step.
- the temperature rising rate in the present specification is calculated from the time taken while the temperature begins to be raised and reaches the highest holding temperature in a calcining device and a temperature difference between the temperature in the calcining furnace of the calcining device at the time of beginning to raise the temperature and the highest holding temperature.
- the precursor in the present embodiment may be a metal composite hydroxide containing Ni, Co, and Al as metal elements.
- the precursor can be produced by the same method as described above (precursor production step: Example 1) except that an aluminum salt solution is used instead of the manganese salt solution.
- aluminum salt that is a solute of the aluminum salt solution
- aluminum sulfate, sodium aluminate, or the like can be used as an aluminum salt that is a solute of the aluminum salt solution.
- the precursor obtained by the above-described step is dried and then mixed with a lithium compound.
- the drying condition of the metal composite oxide or the metal composite hydroxide, which is the precursor is not particularly limited.
- the drying condition may be, for example, any of the following conditions 1) to 3).
- an inert gas such as nitrogen, helium, or argon may be used as the atmosphere during the drying.
- a reducing agent such as hydrazine or sodium sulfite may be used in an inert gas atmosphere during the drying.
- the metal composite oxide or the metal composite hydroxide may be classified as appropriate.
- the LiMO is obtained by calcining a mixture containing the precursor and the lithium compound.
- mixture 1 or mixture 2 is an exemplary example.
- lithium compound any one of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, lithium hydroxide hydrate, and lithium oxide can be used or two or more thereof can be mixed together and used.
- a diamagnetic material is added to the mixture 1 or the mixture 2, and the mixture is calcined in a state where the diamagnetic material is in contact with the mixture 1 or the mixture 2. This makes it possible to produce CAM particles in which a diamagnetic layer is provided on the surface of the ferromagnetic particle.
- an alumina medium or an aluminum medium can be used as the diamagnetic material.
- the alumina medium contains 99% by mass or more of alumina with respect to the total mass of the alumina medium and contains one or more elements selected from Si, K, Na, and Fe as impurities.
- the aluminum medium contains 99% by mass or more of Al with respect to the total mass of the aluminum medium and contains one or more elements selected from Si, K, Na, and Fe as impurities.
- the median values of the volume-based particle diameters of the aluminum medium and the aluminum medium are 2 to 2.2 mm.
- the median value of the volume-based particle diameters is a value that is measured by a sieving method in which a vibrating sieving device is used.
- the amount of the diamagnetic material added is preferably 1% to 10% by mass and more preferably 2% to 9% by mass with respect to the total mass of the mixture 1 or the mixture 2.
- the mode, average value, median value, and standard deviation of the volume magnetic susceptibilities of the CAM particles can be adjusted to the ranges of the present embodiment by adjusting the amount of the diamagnetic material added.
- the upper limit value and lower limit value of the highest holding temperature in the main calcining can be randomly combined together.
- 600°C or higher and 1200°C or lower are exemplary examples.
- the highest holding temperature in the main calcining is set to 600°C or higher and 1200°C or lower and the calcining atmosphere is set to an oxygen atmosphere
- the average value, median value, and standard deviation of the number-based particle diameters of the CAM particles can be controlled to the above-described ranges.
- the calcining temperature in the preliminary calcining or the post calcining may be lower than the calcining temperature in the main calcining, and, for example, a range of 350°C or higher and 700°C or lower is an exemplary example.
- the holding temperature in the calcining may be appropriately adjusted depending on the kind of a transition metal element that is used, a precipitant, or the amount.
- the time during which the mixture is held at the holding temperature 0.1 hour or longer and 20 hours or shorter is an exemplary example, and 0.5 hours or longer and 10 hours or shorter is preferable.
- the temperature rising rate up to the holding temperature is usually 50 °C/hour or faster and 400 °C/hour or slower, and the temperature lowering rate from the holding temperature to room temperature is usually 10 °C/hour or faster and 400 °C/hour or slower.
- the atmosphere for the sintering it is possible to use the atmosphere, oxygen, nitrogen, argon or a gas mixture thereof.
- the obtained calcined product is washed and dried after washing, whereby CAM particles containing Li and Ni are obtained.
- washing liquid As a washing liquid that is used for washing, pure water or an alkaline solution can be used.
- the residual washing liquid is preferably removed by drying.
- CAM particles containing lithium and nickel can be obtained by the above-described step.
- the CAM particles are appropriately crushed and classified.
- the average value, median value, and standard deviation of the number-based particle diameters of the CAM particles can be controlled to the above-described ranges.
- the performance evaluation of the CAM particles can be evaluated with the initial discharge capacity and the initial charge capacity obtained by the following method.
- N-methyl-2-pyrrolidone is used as an organic solvent.
- the positive electrode for a lithium secondary battery produced in the section ⁇ Production of positive electrode for lithium secondary battery> is placed on the lower lid of a part for a coin type battery R2032 (manufactured by Hohsen Corp.) with the aluminum foil surface facing downward, and a separator (polyethylene porous film) is placed on the positive electrode. 300 ⁇ l of an electrolytic solution was poured thereinto.
- lithium metal is used as a negative electrode, and the negative electrode is placed on the upper side of the laminate film separator.
- An upper lid is placed through a gasket and caulked using a caulking machine, thereby producing a lithium secondary battery (coin-type half cell R2032; hereinafter, referred to as the "half cell" in some cases).
- CAM particles for the lithium secondary battery of the present embodiment are preferably composed of the CAM particles for a lithium secondary battery of the present embodiment, but may contain other components as long as the effect of the present invention is not impaired.
- the content proportion of the CAM particles for a lithium secondary battery of the present embodiment with respect to the total mass (100% by mass) of the CAM particles for the lithium secondary battery is preferably 70% to 99% by mass and more preferably 80% to 98% by mass.
- An example of the lithium secondary battery of the present embodiment includes a positive electrode, a negative electrode, a separator sandwiched between the positive electrode and the negative electrode, and an electrolytic solution disposed between the positive electrode and the negative electrode.
- Fig. 1A and Fig. 1B are schematic views illustrating an example of the lithium secondary battery of the present embodiment.
- a cylindrical lithium secondary battery 10 of the present embodiment is produced as described below.
- a pair of separators 1 having a strip shape, a stripshaped positive electrode 2 having a positive electrode lead 21 at one end, and a stripshaped negative electrode 3 having a negative electrode lead 31 at one end are laminated in the order of the separator 1, the positive electrode 2, the separator 1, and the negative electrode 3 and are wound to form an electrode group 4.
- the electrode group 4 and an insulator are accommodated in a battery can 5, and then the can bottom is sealed.
- the electrode group 4 is impregnated with an electrolytic solution 6, and an electrolyte is disposed between the positive electrode 2 and the negative electrode 3.
- the upper portion of the battery can 5 is sealed with a top insulator 7 and a sealing body 8, whereby the lithium secondary battery 10 can be produced.
- the shape of the electrode group 4 for example, a columnar shape in which the cross-sectional shape becomes a circle, an ellipse, a rectangle, or a rectangle with rounded corners when the electrode group 4 is cut in a direction perpendicular to the winding axis is an exemplary example.
- a shape of the lithium secondary battery having the electrode group 4 a shape specified by IEC60086, which is a standard for a battery specified by the International Electrotechnical Commission (IEC), or by JIS C 8500 can be adopted.
- IEC60086 which is a standard for a battery specified by the International Electrotechnical Commission (IEC), or by JIS C 8500
- shapes such as a cylindrical shape and a square shape can be exemplary examples.
- the lithium secondary battery is not limited to the winding-type configuration and may be a laminate-type configuration in which the laminated structure of the positive electrode, the separator, the negative electrode, and the separator is repeatedly overlaid.
- a so-called coin-type battery, button-type battery, or paper-type (or sheet-type) battery can be an exemplary example.
- a positive electrode of the present embodiment can be produced by first adjusting a positive electrode mixture containing a CAM, a conductive material, and a binder and supporting the positive electrode mixture by a positive electrode current collector.
- a carbon material can be used as the conductive material in the positive electrode of the present embodiment.
- a carbon material graphite powder, carbon black (for example, acetylene black), a fibrous carbon material, and the like can be exemplary examples.
- the proportion of the conductive material in the positive electrode mixture is preferably 5 to 20 parts by mass with respect to 100 parts by mass of the CAM.
- thermoplastic resin As the binder in the positive electrode, a thermoplastic resin can be used.
- thermoplastic resin polyimide resins; fluororesins such as polyvinylidene fluoride (hereinafter, referred to as PVdF in some cases) and polytetrafluoroethylene; polyolefin resins such as polyethylene and polypropylene, and the resins described in WO 2019/098384A1 or US2020/0274158A1 can be exemplary examples.
- thermoplastic resins Two or more of these thermoplastic resins may be used in a mixture form.
- a fluororesin and a polyolefin resin are used as the binder, the proportion of the fluororesin in the entire positive electrode mixture is set to 1 mass% or more and 10 mass% or less, and the proportion of the polyolefin resin is set to 0.1 mass% or more and 2 mass% or less, whereby it is possible to obtain a positive electrode mixture having both a high adhesive force to the positive electrode current collector and a high bonding force inside the positive electrode mixture.
- a stripshaped member formed of a metal material such as Al, Ni, or stainless steel as a forming material can be used as the positive electrode current collector in the positive electrode.
- a method for supporting the positive electrode mixture by the positive electrode current collector a method in which a paste of the positive electrode mixture is prepared using an organic solvent, the paste of the positive electrode mixture to be obtained is applied to and dried on at least one surface side of the positive electrode current collector, and the positive electrode mixture is fixed by pressing is an exemplary example.
- the separator in the lithium secondary battery it is possible to use, for example, a material that is made of a material such as a polyolefin resin such as polyethylene or polypropylene, a fluororesin, or a nitrogen-containing aromatic polymer and has a form such as a porous film, a non-woven fabric, or a woven fabric.
- the separator may be formed using two or more of these materials or the separator may be formed by laminating these materials.
- the separators described in JP-A-2000-030686 or US20090111025A1 may be used.
- the electrolytic solution in the lithium secondary battery of the present embodiment contains an electrolyte and an organic solvent.
- lithium salts such as LiClO 4 and LiPF 6 are exemplary examples, and a mixture of two or more thereof may be used.
- electrolytes described in WO 2019/098384A1 or US2020/0274158A1 may be used.
- organic solvent that is contained in the electrolytic solution for example, carbonates such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate can be used.
- organic solvents described in WO2019/098384A1 or US2020/0274158A1 can be used as the organic solvent that is contained in the electrolytic solution.
- organic solvent two or more of these are preferably mixed and used, and a solvent mixture of a cyclic carbonate and a non-cyclic carbonate and a solvent mixture of a cyclic carbonate and ethers are more preferable.
- electrolytic solution it is preferable to use an electrolytic solution containing a lithium salt containing fluorine such as LiPF 6 and an organic solvent having a fluorine substituent since the safety of lithium secondary batteries to be obtained is enhanced.
- a lithium salt containing fluorine such as LiPF 6
- an organic solvent having a fluorine substituent since the safety of lithium secondary batteries to be obtained is enhanced.
- the electrolyte and the organic solvent that are contained in the electrolytic solution the electrolytes and the organic solvents described in WO2019/098384A1 or US2020/0274158A1 may be used.
- the positive electrode having such a configuration have the CAM particles with the above-described configuration, it is possible to improve the charge capacity and the discharge capacity of the lithium secondary battery.
- the all-solid-state lithium-ion secondary battery 1000 is shown in the drawings to have one laminate 100, but is not limited thereto.
- the all-solid-state lithium-ion secondary battery 1000 may have a configuration in which the laminate 100 is used as a unit cell and a plurality of unit cells (laminates 100) is sealed inside the exterior body 200.
- the positive electrode 110 has a positive electrode active material layer 111 and a positive electrode current collector 112.
- the positive electrode active material layer 111 contains the CAM particles, which are one aspect of the present invention described above.
- the positive electrode active material layer 111 may contain a solid electrolyte, a conductive material, and a binder.
- solid electrolyte that the positive electrode active material layer 111 may have, a solid electrolyte that is lithium ion-conductive and used in well-known all-solid-state batteries can be adopted.
- solid electrolyte an inorganic electrolyte and an organic electrolyte can be exemplary examples.
- inorganic electrolyte an oxide-based solid electrolyte, a sulfide-based solid electrolyte, and a hydride-based solid electrolyte can be exemplary examples.
- organic electrolyte polymer-based solid electrolytes are exemplary examples.
- Li 2 S-P 2 S 5 -based compounds Li 2 S-SiS 2 based compounds, Li 2 S-GeS 2 -based compounds, Li 2 S-B 2 S 3 -based compounds, Li 2 S-P 2 S 3 -based compounds, LiI-Si 2 S-P 2 S 5 -based compounds, LiI-Li 2 S-P 2 O 5 -based compounds, LiI-Li 3 PO 4 -P 2 S 5 -based compounds, Li 10 GeP 2 Si 2 , and the like can be exemplary examples.
- the proportion of P 2 S 5 that is contained in the Li 2 S-P 2 S 5 -based compound is, for example, 10 to 50 mass% with respect to the entire Li 2 S-P 2 S 5 -based compound.
- the proportion of the different raw material that is contained in the Li 2 S-P 2 S 5 -based compound is, for example, 0 to 30 mass% with respect to the entire Li 2 S-P 2 S 5 -based compound.
- the Li 2 S-P 2 S 5 -based compounds also include solid electrolytes containing Li 2 S and P 2 S 5 in different mixing ratios.
- Li 2 S-SiS 2 -based compounds Li 2 S-SiS 2 , Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -LiBr, Li 2 S-SiS 2 -LiCl, Li 2 S-SiS 2 -B 2 S 3 -LiI, Li 2 S-SiS 2 -P 2 S 5 -LiI, Li 2 S-SiS 2 -P 2 S 5 -LiCl, and the like are exemplary examples.
- Li 2 S-GeS 2 -based compounds Li 2 S-GeS 2 , Li 2 S-GeS 2 -P 2 S 5 , and the like are exemplary examples.
- the sulfide-based solid electrolyte may be a crystalline material or an amorphous (amorphous) material.
- Two or more solid electrolytes can be jointly used as long as the effect of the invention is not impaired.
- the materials described in the above-described (conductive material) can be used.
- the proportion of the conductive material in the positive electrode mixture the proportions described in the above-described (conductive material) can be applied in the same manner.
- the binder that the positive electrode has the materials described in the above-described (binder) can be used.
- a method for supporting the positive electrode active material layer 111 by the positive electrode current collector 112 a method in which the positive electrode active material layer 111 is formed by pressurization on the positive electrode current collector 112 is an exemplary example.
- a cold press or a hot press can be used for the pressurization.
- the positive electrode active material layer 111 may be supported by the positive electrode current collector 112 by preparing a paste of a mixture of the CAM, the solid electrolyte, the conductive material, and the binder using an organic solvent to produce a positive electrode mixture, applying and drying the positive electrode mixture to be obtained on at least one surface side of the positive electrode current collector 112, and fixing the positive electrode mixture by pressing.
- the positive electrode active material layer 111 may be supported by the positive electrode current collector 112 by preparing a paste of a mixture of the CAM, the solid electrolyte, and the conductive material using an organic solvent to produce a positive electrode mixture, applying and drying the positive electrode mixture to be obtained on at least one surface side of the positive electrode current collector 112, and sintering the positive electrode mixture.
- the organic solvent that can be used for the positive electrode mixture the same organic solvent as the organic solvent that can be used in the case of preparing the paste of the positive electrode mixture described in the above-described (positive electrode current collector) can be used.
- the positive electrode 110 can be produced by the method described above.
- the negative electrode 120 has a negative electrode active material layer 121 and the negative electrode current collector 122.
- the negative electrode active material layer 121 contains a negative electrode active material.
- the negative electrode active material layer 121 may contain a solid electrolyte and a conductive material.
- the negative electrode active material, the negative electrode current collector, the solid electrolyte, the conductive material, and a binder, those described above can be used.
- a method for supporting the negative electrode active material layer 121 by the negative electrode current collector 122 similar to the case of the positive electrode 110, a method in which the negative electrode active material layer 121 is formed by pressurization, a method in which a paste-form negative electrode mixture containing a negative electrode active material is applied and dried on the negative electrode current collector 122 and then the negative electrode active material layer 121 is compressed by pressing, and a method in which a paste-form negative electrode mixture containing a negative electrode active material is applied, dried and then sintered on the negative electrode current collector 122 are exemplary examples.
- the solid electrolyte layer 130 has the above-described solid electrolyte.
- the solid electrolyte layer 130 can be formed by depositing a solid electrolyte of an inorganic substance on the surface of the positive electrode active material layer 111 in the above-described positive electrode 110 by a sputtering method.
- the laminate 100 can be produced by laminating the negative electrode 120 on the solid electrolyte layer 130 provided on the positive electrode 110 as described above using a well-known method such that the negative electrode electrolyte layer 121 comes into contact with the surface of the solid electrolyte layer 130.
- the positive electrode active material for an all-solid-state lithium-ion battery having the above-described configuration, it is possible to smoothly exchange lithium ions between the positive electrode and the solid electrolyte and to improve the battery characteristics.
- the all-solid-state lithium-ion battery since the all-solid-state lithium-ion battery has the positive electrode active material for an all-solid-state lithium-ion battery, it is possible to improve the battery characteristics of the all-solid-state lithium-ion battery.
- the present invention also includes the following aspects.
- CAM particles for a lithium secondary battery containing at least Li and Ni in which, when a volume magnetic susceptibility of one whole particle of the CAM particles for a lithium secondary battery is obtained in each of a plurality of the particles, a mode of individual volume magnetic susceptibilities in a range of 0.004 or more and 0.04 or less is 0.0043 or more and 0.0117 or less.
- composition analysis of CAM particles to be produced by a method to be described below was carried out using an ICP emission spectroscopic analyzer (SPS 3000, manufactured by Seiko Instruments Inc.) after a powder the obtained CAM particles was dissolved in hydrochloric acid.
- SPS 3000 ICP emission spectroscopic analyzer
- X p is the volume magnetic susceptibility of the CAM particle.
- X m is the volume magnetic susceptibility of the medium, ⁇ is the coefficient of viscosity, ⁇ 0 is the magnetic permeability of the vacuum.
- B is the magnetic flux density.
- r is the radius of the CAM particle.
- v is the magnetic migration velocity of the moving CAM particle.
- NANOMEASURE KNM-001 manufactured by Yamato Scientific Co., Ltd. was used.
- the average value, median value, and standard deviation of 1000 CAM particles were obtained using the value of each of the obtained number-based particle diameters.
- the median value of the volume-based particle diameters of an alumina medium was calculated by a sieving method with a vibrating sieving device.
- a vibrating sieving device a circular vibrating sieve (KIC type 1200 type) manufactured by Kowa Kogyosho Co., Ltd. was used.
- lithium metal was used as a negative electrode, and the negative electrode was placed on the upper side of the laminate film separator.
- An upper lid was placed through a gasket and caulked using a caulking machine, thereby producing a lithium secondary battery (coin-type half cell R2032; hereinafter, referred to as the "half cell" in some cases).
- the initial charge capacity and the initial discharge capacity were measured by the above-described method for measuring the "initial charge capacity" and the "initial discharge capacity”.
- a nickel sulfate aqueous solution, a cobalt sulfate aqueous solution, and a manganese sulfate aqueous solution were mixed in proportions in which the atom ratio of nickel atoms, cobalt atoms, and manganese atoms reached 85:10:5, thereby obtaining a raw material liquid mixture.
- the nickel cobalt manganese composite hydroxide 1 and a lithium hydroxide monohydrate powder were weighed in proportions in which Li/(Ni + Co + Mn) reached 1.10.
- Potassium sulfate which was an inert melting agent, was weighed in a proportion in which the mole ratio of potassium sulfate to the lithium hydroxide monohydrate powder reached 0.1.
- the nickel cobalt manganese composite hydroxide 1, the lithium hydroxide monohydrate powder, and potassium sulfate were mixed in a crucible, thereby obtaining a mixture 1.
- An alumina medium was added to the obtained mixture 1 at a mass ratio of 5% by mass and mixed.
- the alumina medium contained 99% by mass or more of alumina with respect to the total mass of the alumina medium and contained Si, K, Na, and Fe as main impurities.
- the median value of the volume-based particle diameters of the alumina medium was 2.0 mm.
- a powder of CAM particles 2 was obtained by the same method as in Example 1 except that an aluminum medium containing 5% by mass of an aluminum element in terms of the weight ratio was added to the mixture 1 at a mass ratio of 15% by mass.
- a nickel sulfate aqueous solution, a cobalt sulfate aqueous solution, and an aluminum sulfate aqueous solution were mixed in proportions in which the atom ratio of nickel atoms, cobalt atoms, and aluminum atoms reached 88:9:3, thereby obtaining a raw material liquid mixture.
- the nickel cobalt aluminum composite hydroxide 1 and a lithium hydroxide monohydrate powder were weighed in proportions in which Li/(Ni + Co + Mn) reached 1.10.
- the nickel cobalt aluminum composite hydroxide 1 and the lithium hydroxide monohydrate powder were mixed in a crucible, thereby obtaining a mixture 2.
- the alumina medium that was used in Example 1 was added to the obtained mixture 2 at a mass ratio of 5% by mass and mixed.
- a powder of CAM particles 5 was obtained by the same method as in Example 1 except that neither an alumina medium nor an aluminum medium was added.
- the present invention it is possible to provide positive electrode active material particles for a lithium secondary battery, a positive electrode for a lithium secondary battery, and a lithium secondary battery in which lithium ions can smoothly migrate and with which the battery characteristics of the lithium secondary battery can be improved.
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PCT/JP2021/015128 WO2021210524A1 (fr) | 2020-04-14 | 2021-04-12 | Particules de matériau actif d'électrode positive pour batterie secondaire au lithium, électrode positive pour batterie secondaire au lithium, et batterie secondaire au lithium |
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- 2021-04-12 US US17/918,489 patent/US20230142293A1/en active Pending
- 2021-04-12 CN CN202180027977.0A patent/CN115398677A/zh active Pending
- 2021-04-12 WO PCT/JP2021/015128 patent/WO2021210524A1/fr unknown
- 2021-04-12 KR KR1020227035386A patent/KR20230002399A/ko active Search and Examination
- 2021-04-12 EP EP21788988.0A patent/EP4138159A1/fr active Pending
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Also Published As
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KR20230002399A (ko) | 2023-01-05 |
JP6861870B1 (ja) | 2021-04-21 |
CN115398677A (zh) | 2022-11-25 |
WO2021210524A1 (fr) | 2021-10-21 |
JP2021170437A (ja) | 2021-10-28 |
US20230142293A1 (en) | 2023-05-11 |
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